Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C37/00—Component parts, details, accessories or auxiliary operations, not covered by group B29C33/00 or B29C35/00
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
  • B29D11/00—Producing optical elements, e.g. lenses or prisms
  • B29D11/00009—Production of simple or compound lenses
  • B29D11/00038—Production of contact lenses
  • B29D11/00125—Auxiliary operations, e.g. removing oxygen from the mould, conveying moulds from a storage to the production line in an inert atmosphere
  • B29D11/00192—Demoulding, e.g. separating lenses from mould halves
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B08—CLEANING
  • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
  • B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
  • B08B3/04—Cleaning involving contact with liquid
  • B08B3/10—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration
  • B08B3/102—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration with means for agitating the liquid
  • B08B3/104—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration with means for agitating the liquid using propellers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B08—CLEANING
  • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
  • B08B7/00—Cleaning by methods not provided for in a single other subclass or a single group in this subclass
  • B08B7/0021—Cleaning by methods not provided for in a single other subclass or a single group in this subclass by liquid gases or supercritical fluids
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C37/00—Component parts, details, accessories or auxiliary operations, not covered by group B29C33/00 or B29C35/00
  • B29C37/0003—Discharging moulded articles from the mould
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
  • B29C71/009—After-treatment of articles without altering their shape; Apparatus therefor using gases without chemical reaction
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
  • B29D11/00—Producing optical elements, e.g. lenses or prisms
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
  • B29D11/00—Producing optical elements, e.g. lenses or prisms
  • B29D11/00009—Production of simple or compound lenses
  • B29D11/00038—Production of contact lenses
  • B29D11/00076—Production of contact lenses enabling passage of fluids, e.g. oxygen, tears, between the area under the lens and the lens exterior
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
  • B29C71/0009—After-treatment of articles without altering their shape; Apparatus therefor using liquids, e.g. solvents, swelling agents
  • B29C2071/0027—Removing undesirable residual components, e.g. solvents, unreacted monomers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
  • B29C71/0009—After-treatment of articles without altering their shape; Apparatus therefor using liquids, e.g. solvents, swelling agents
  • B29C2071/0054—Supercritical fluid treatment, i.e. using a liquid in which distinct liquid and gas phases do not exist
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
  • B29L2011/00—Optical elements, e.g. lenses, prisms
  • B29L2011/0016—Lenses
  • B29L2011/0041—Contact lenses
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
  • B29L2031/00—Other particular articles
  • B29L2031/753—Medical equipment; Accessories therefor

Definitions

• This invention relates broadly to extraction and cleaning of polymeric articles and mold separation processes. More specifically, this invention relates to molded-lens extraction, cleaning and deblocking processes.
• porous sponges of biodegradable polymers have been formed by applying supercritical fluids in a manner requiring a sharp pressure drop (See PCT InL AppI. No. WO 9109079, De Ponti).
• the efficient use of supercritical fluids requires high temperatures and pressures, which may damage certain polymeric materials.
• Numerous polymeric articles are formed by placing a monomeric solution into a mold and then initiating polymerization.
• the efficient removal of molded articles from the mold represents a critical step in the design of a manufacturing process. After the polymeric article is separated from the mold, the article must typically be subjected to extraction processes to remove undesirable materials, such as unreacted or partially-reacted monomers (i.e., oligomers or short chain polymers) and residual solvent.
• An ophthalmic lens is an example of a polymeric article which may be molded in such a manner.
• Ophthalmic lenses such as contact lenses
• contact lenses are typically formed from hydrophilic monomers, in order to enhance biocompatibility with the eye.
• Contact lenses formed from hydrophilic polymers are desirable, in part, because hydrophilic contact lenses move well on the eye. This movement enhances tear flow and debris removal beneath the lens, thereby improving patient comfort.
• One method of forming a contact lens involves lathing the lens from a preformed polymeric disc, a so-called lens "button".
• Another method of forming contact lenses involves placing a monomeric solution into a lens mold and polymerizing the monomer. Double-sided molding is an example of the second type of lens molding process which has been gaining in popularity in recent times.
• the lenses are typically "deblocked", i.e., separated from the mold, and subjected to extraction processes for a period of hours.
• the extraction processes remove unreacted monomer and partially-reacted oligomer, solvents or other undesirable materials.
• These commercial extraction processes typically involve contacting the lenses with organic solvents, such as isopropyl alcohol, to solvate the undesireables.
• organic solvents such as isopropyl alcohol
• the step of deblocking the lens presents manufacturing problems.
• the deblocking must occur quickly and consistently, in order to maximize production efficiency.
• the deblocking must be complete, i.e., even minor portions of the polymeric lens must not remain adhered to the mold. Incomplete blocking typically results in substantial volumes of production scrap because the lens is likely to tear when removed from the mold.
• even slight lens surface imperfections, caused by the lens adhering to the mold during deblocking translate into major visual distortions for the lens wearer.
• An object of the invention is to provide a method of extracting undesirable materials from a polymeric article and/or cleaning from the surface of a polymeric article any undesirable materials which have adhered to the surface without introducing excessive organic solvents.
• Another object of the invention is to provide a method of quickly and efficiently deblocking a polymeric article from a mold subsequent to formation of the polymeric article by polymerization in the mold.
• a further object of the invention is to provide a method for simultaneously removing undesirable materials from a polymeric article and deblocking a polymeric article from a mold.
• Yet another object of this invention is to reduce production time required to process polymeric articles.
• An additional object of the invention is to reduce production scrap in the production of polymeric articles.
• Even another object of this invention is to reduce the amount of organic solvents required to produce polymeric articles.
• One embodiment of the invention is a method of removing undesirable materials from hydrophilic polymeric articles.
• the method involves contacting the polymeric article with a supercritical fluid at conditions and for a time sufficient to remove undesirable materials from the polymeric article.
• the removal may involve extraction of undesirable materials from the polymeric core or cleaning of undesirable materials from the surface of the polymer.
• ophthalmic lenses are contacted with supercritical fluid, especially supercritical fluids containing carbon dioxide, to remove monomers, oligomers, and/or solvents remaining from the preceding lens-polymerization process.
• Another embodiment is a method of deblocking polymeric articles from molds subsequent to polymerization processes.
• the method includes the step of contacting the polymeric article with a supercritical fluid at conditions and for a time sufficient to separate the polymeric article from the mold.
• a preferred embodiment is a method of deblocking ophthalmic lenses from molds subsequent to the lens-polymerization process by contacting the lens with a supercritical fluid, preferably one which includes carbon dioxide.
• a method of simultaneously removing undesirable materials from a polymeric article and deblocking a polymeric article from a mold includes a step of contacting the polymeric article with supercritical fluid at conditions and for a time sufficient to both remove certain undesirable materials from the polymeric article and separate the polymeric article from the mold.
• FIG. 1 is a side sectional view of a multicomponent, batch-process, supercritical-fluid treatment apparatus.
• FIG. 2 is a side sectional view of an in-line, supercritical-fluid treatment apparatus.
• the present innovative methods of extracting undesirable materials from a polymeric article, deblocking a polymeric article from a mold, and/or cleaning undesirable materials from the surface of a polymeric article involve the steps of:
• a "supercritical fluid”, as the term is used herein, means a substance at a temperature and pressure which places the substance in or near the supercritical regime.
• a temperature of at least about 20°C and a pressure at least about 600 psia are believed to be sufficient to achieve the advantages of the present invention.
• Removing undesirable materials means either extracting undesirable materials from the polymeric core or cleaning undesirable materials from the surface of the polymeric article.
• Undesirable materials which may be extracted include monomers, partially-reacted oligomers, solvents, polymerization initiators, and the like.
• Undesirable materials which may be cleaned from the surface of the polymeric article include the aforementioned-undesirable materials, debris or surface contaminants, such as abrasives used in surface polishing processes, oils, and the like.
• polymeric articles which are treated with supercritical fluids are essentially "dry", i.e. free of solvent after SCF treatment, while organic solvent extraction, cleaning or deblocking processes yield "wet” products, i.e., some solvent remains in or on the article.
• SCF supercritical fluids
• the article In order to further process a polymeric article which is "wet", the article must be dried over a period of time, and typically, at an elevated temperature.
• polymeric articles which have been subjected to SCF treatment may be nearly immediately indexed or moved to the next processing step (e.g., a subsequent surface treatment process).
• Another advantage of the present invention is that the use of flammable, potentially toxic, organic solvents is minimized or eliminated.
• the invention increases safety in the manufacturing environment and/or reduces costs associated with protecting workers from the hazards of organic solvents.
• the expenses and hazards associated with disposal of spent organic solvents is reduced or eliminated with the present invention.
• the instant invention offers yet another advantage in improving extraction efficiency.
• extraction of contact lenses with supercritical fluids in accordance with the instant teachings may yield monomer/oligomer concentrations less than about 2 weight percent in a 1.5 to 3 hour time period using a 95 weight percent isopropyl alcohol / 5 weight percent carbon dioxide SCF mixture at about a one gallon per minute flow rate.
• extraction of contact lenses with solvent typically yields monomer/oligomer concentrations at about 2% in a 24 hour time period.
• the present SCF extraction process yields the same quality product in a greatly reduced time frame.
• the present invention is particularly suited to application in those areas which have restrictive regulatory requirements, especially in the ophthalmic lens industry.
• Polymeric articles which may be treated with supercritical fluids in accordance with the present invention include a wide variety of polymeric articles which are formed by initiating polymerization of a monomeric mixture in a mold.
• polymeric articles include, without limitation thereto, medical devices and components, such as drug delivery devices (transdermal, ophthalmic, parenteral, etc.) and components thereof; and, in particular, ophthalmic devices including vision correction devices, such as contact lenses, ocular implants, ocular onlays, and components thereof.
• Polymers suited to the formation of polymeric articles which may be advantageously subjected to the presently described inventive processes include, without limitation thereto, hydrophobic polymers, such as polyethylene, polypropylene, poly(vinyl pyrrolidone) or polysiloxanes; hydrophilic polymers, such as poly(2-hydroxyethyl methacrylate), and poly(vinyl alcohol); biodegradable polymers such as polylactides, polyglycolides, and the like; and antimicrobial polymers such as polyquatemary ammonium compounds.
• the SCF treatment processes of the present invention are applied to hydrophilic polymeric articles, capable of forming hydrogels when equilibrated with water (i.e., capable of absorbing about 10 weight percent water or more).
• the SCF treatment processes of the present invention are preferably applied to contact lenses which are the copolymerization product of a copolymerizable macromer and two or more copolymerizable monomers.
• the copolymerizable macromer is advantageously a macromer comprising a polysiloxane segment, even more preferred a polydimethylsiloxane segment.
• Said macromer also preferred, comprises in addition urethane linkages and two or up to five terminal vinylic groups which are suitable for a polymerization reaction with the copolymerizable monomers.
• a most preferred macromer comprises a polydimethylsiloxane segment to which a vinylic isocyanate is bonded, such as isocyanatoethylmethacrylate (I EM).
• the macromer may comprise other segments not yet mentioned specifically. [Examples for such segments are perfluoropolyether segments, diisocyanates, or derivatives of gluconic acid.
• the first type of copolymerizable monomer used jointly with said macromer is a monovinylic siloxane having up to 15 silicon atoms.
• a preferred example is 3-tris(trimethylsiloxy)silyl- propyl methacrylate (TRIS).
• the second type of copolymerizable monomer used jointly with said macromer is a hydrophilic copolymerizable monomer as usually used in the manufacture of contact lenses.
• Typical examples are hydroxy-C r C4-alkyl (meth)acrylates, such as 2-hydroxyethyl methacrylate, (meth)acrylic acid, dimethylacrylamide or N-vinyl pyrrolidone, of which dimethylacrylamide (DMA) is especially preferred.
• the mixture of macromer, monomer of the first type and monomer of the second type typically comprises, in percent by weight, macromer: about 30 to 60 %, monomer of the first type: about 12.5 to 35 %, monomer of the second type: about 27.5 to 35 %.
• the mixture comprises, in percent by weight: macromer about 33 to 56 %, monomer of the first type: about 14 to 33 %, monomer of the second type: about 30 to 33 %.
• Three examples of very preferred mixtures comprise about 50 % of macromer, 20 % of monomer of the first type and 30 % of the second type; 56 % of macromer, 14 % of monomer of the first type and 30 % of the second type; 33 % of macromer, 33 % of monomer of the first type and 33 % of the second type;
• the monomer of the first type is most preferably TRIS and the monomer of the second type is most preferably DMA.
• contact lenses which are molded in a double-sided molding process are typically molded in a hydrophobic polymer mold.
• a monomeric mixture which commonly includes 2-hydroxyethyl methacrylate for hydrophilic "soft" contact lenses, is introduced into the mold.
• the mold containing the monomer may be irradiated to initiate polymerization.
• the lens Once the lens has been formed, i.e., polymerization is substantially complete, the lens must be removed, i.e., deblocked, from the mold. At times, lenses are scrapped because of damage caused during deblocking steps, since the adhesion of the lens to the mold impairs the deblocking process.
• unreacted monomer and oligomers are undesirable materials which must be removed from the lens. Removal of undesirable materials may involve numerous subsequent processing steps, including solvent extraction and heat treating over extended time periods. Thus, many commercial contact lens production processes include numerous processing steps relating to extraction and deblocking.
• a simultaneous extraction and deblocking step may be substituted for the prior art sequential extraction and deblocking steps. It has been unexpectedly found that the application of supercritical fluid to a contact lens in a mold for extraction purposes causes the lens to detach from the mold. This reduction in the attractive forces between the lens and the mold enables a quick removal of the lens from the mold, while minimizing the likelihood of lens damage and concomitant scrap formation.
• the supercritical substance may be selected from a wide variety of substances which are gases or liquids at room temperature and pressure, including without limitation thereto, carbon dioxide; water; alcohols, especially low molecular weight alcohols such as isopropyl alcohol and ethanol; ammonia; ethylene; carbon disulfide; sulfurhexafluoride; hexane; acetone; and other common organic solvents, and mixtures thereof.
• a preferred group of SCF's includes alcohols such as isopropyl alcohol and relatively inert, inoccuous gases or fluids such as carbon dioxide or water. Carbon dioxide and isopropyl alcohol are more preferred.
• the substance used as the supercritical fluid must be at a temperature and pressure which places the substance in or near the supercritical region.
• the temperature and pressure of the supercritical fluid depend on the chosen fluid composition.
• the temperature and pressure for producing a supercritical fluid are above about 1085 psi and about 31 °C.
• a temperature range of 21 to 45°C and pressure range of 600 to 5000 psia are believed useful for a carbon dioxide stream.
• the carbon dioxide stream is maintained at a temperature of about 21 to 35°C and a pressure of about 900 to 3000 psia.
• Particularly preferred mixtures of fluids useful in extracting and deblocking contact lenses include carbon dioxide and isopropyl alcohol (IPA).
• a preferred composition of the fluid includes about 70 to about 99 weight percent carbon dioxide and about 1 to about 30 weight percent isopropyl alcohol.
• a more preferred fluid composition includes about 75 to about 85 weight percent carbon dioxide and about 15 to about 25 weight percent isopropyl alcohol.
• the supercritical fluid In order to properly extract undesirable materials from a contact lens within a lens mold, the supercritical fluid should be properly agitated. Sufficient agitation of the supercritical fluid may occur by merely contacting a stream of supercritical fluid with the polymeric article to be treated. However, a preferred flow regime is in the turbulent range, i.e., fluid flows having Reynold's numbers above 2100.
• Supercritical fluid extraction equipment may be procured commercially from a variety of sources, including Pressure Products Industries, Inc. (Warminster, Pennsylvania) and Autoclave Engineering (Erie, Pennsylvania).
• a preferred SCF extractor for opthalmic devices, such as contact lenses, is the EP Model 12-3000, available from Autoclave Engineering.
• the invention is a method for treating an ophthlamic lens subsequent to the polymerization of the lens.
• This embodiment of the invention is discussed with respect to a particularly preferred embodiment - the treatment of a contact lens.
• this embodiment of the invention is not limited to contact lenses, but includes intraocular lenses, drug delivery lenses, comeal onlays, etc.
• trie lens is fabricated by a double-sided molding process
• one half of the mold is separated from the lens prior to application of supercritical fluid.
• the lens remains removably affixed to the base mold half (convex mold half), leaving the front or convex lens surface exposed.
• the lens mold may be treated in order to render one mold half more adherent and/or the other mold half less adherent, in order to ensure consistent location of the lens on the desired mold half.
• sensing equipment may be used to determine the mold half to which the lens is removably-affixed, so that the lens-containing mold half is treated with the supercritical fluid. Regardless of the technique chosen, the lens-retaining mold half is treated with supercritical fluid subsequent to the first mold half separation step.
• FIG. 1 schematically illustrates an apparatus capable of batch treating a plurality of lenses.
• lens-treating apparatus 10 is surrounded with insulation 12 sufficient to maintain the applied fluid at the desired supercritical temperature and pressure ranges.
• Trays 14 support a plurality of lenses 16 affixed to molds 18.
• the support trays either have perforations or are sufficiently porous to allow supercritical fluid to flow through the trays.
• the trays are loaded into lens treating apparatus 10, either manually or via an automated lens distribution system, through an access opening (not shown), with the access opening being sealed subsequent to the loading step.
• Supercritical fluid entering through inlet 20 at a rate of about 0.1 to 5 gallons per minute, is distributed uniformly to passageways positioned along the walls of the container by agitation means 22.
• supercritical fluid passes through a flow distribution member 24, which provides uniform supercritical fluid flow across a cross-section of the apparatus perpendicular to the flow.
• the supercritical fluid flows through trays 14, contacting lenses 16 and molds 18, preferably in a turbulent fashion, before exiting through the fluid outlet (not shown).
• FIG. 2 An alternative lens treating apparatus 40 is illustrated in FIG. 2.
• Apparatus 40 shown in closed configuation, includes inlet 42 on upper portion 44 and outlet 46 on lower portion 48.
• Apparatus 40 further includes agitation means 50 and peripheral sealing means 52.
• upper and lower portions 44 and 48 are vertically separated to allow lens 54 affixed to mold 56 to index on conveyor 58 to a position between the upper and lower portions. After a lens-containing mold is indexed to the desired position intermediate upper and lower portions 44 and 48, the upper and lower portions are mated, thereby forming a liquid impermeable seal defined by peripheral sealing means 52.
• Supercritical fluid flows through inlet 42 and is dispersed by agitating means 50, thereby contacting the lens in a turbulent fashion.
• agitation is provided by mechanical means, as shown in FIGS. 1 and 2.
• a preferred agitation state may arise merely from the application of the supercritical fluid at the appropriate pressure, i.e., a turbulent flow is developed by the passageway dimensions, passageway shape, and fluid pressure.
• FIGS. 1 and 2 present two designs for equipment suited to treating lenses with supercritical fluids.
• FIGS. 1 and 2 present two designs for equipment suited to treating lenses with supercritical fluids.
• FIGS. 1 and 2 present two designs for equipment suited to treating lenses with supercritical fluids.
• a wide variety of alternatives will be readily apparent to persons having ordinary skill in the art, given the teachings of the present invention. Accordingly, the invention should not be strictly constrained to the designs presented in FIGS. 1 and 2.
• EXAMPLE I Hydrophilic contact lens are formed in a double-sided molding process.
• the concave mold halves are manually removed, leaving the lenses predominately affixed to the convex mold halves.
• the lenses and affixed convex mold halves are placed inside the treatment cavity of an Autoclave Engineering model EP-2000 Supercritical CO2 Treatment System. Supercritical carbon dioxide fluid at 3000 psig and 35°C is applied to the lenses and affixed mold halves for a period of about 100 minutes.
• the lenses affixed to the base- curve mold halves are not deblocked from the mold halves.
• EXAMPLE II Hydrophilic contact lenses and affixed mold halves are treated as described in Example I, with the SCF pressure at 3000 psig and temperature at 30°C. The treatment period is about 100 minutes. The lenses affixed to the base-curve mold halves are not deblocked from the mold halves.
• EXAMPLE III Hydrophilic contact lenses and affixed mold halves are treated as described in -Example I, with the SCF pressure at 3000 psig and temperature at 25°C. The treatment period is about 100 minutes. The lenses are partially, but incompletely, deblocked from the base-curve mold halves.
• EXAMPLE IV Hydrophilic contact lenses and affixed mold halves are treated as described in Example I, with the near-supercritical fluid pressure at 1000 psig and temperature at 25°C. The treatment period is about 100 minutes. The lenses are partially, but incompletely, deblocked from the base-curve mold halves.
• EXAMPLE V Hydrophilic contact lenses and affixed mold halves are treated as described in EExample I, but a 19 weight percent isopropyl alcohol (IPA) / 81 weight percent carbon dioxide mixture is used, instead of the 100% carbon dioxide of -Example I.
• the pressure is 3000 psig while the temperature was 30°C.
• the treatment period is about 97 minutes.
• the lenses are deblocked from the base-curve mold halves.
• EXAMPLE VI Hydrophilic contact lenses and affixed mold halves are treated as described in (Example I, but a 14 weight percent isopropyl alcohol / 86 weight percent carbon dioxide mixture is used, instead of the 100% carbon dioxide of Example I.
• the pressure is pulsed while the temperature is held at about 30°C.
• the pressure cycle includes about a 10 minute period at 3000 psig followed by a pressure drop to about 1000 psig, then a return to the 3000 psig pressure.
• the treatment period is about 81 minutes.
• the lenses are deblocked from the base-curve mold halves.
• EXAMPLE VII Hydrophilic contact lenses and affixed mold halves are treated as described in EExample I, but a 10 weight percent isopropyl alcohol / 90 weight percent carbon dioxide SCF mixture is used, instead of the 100% carbon dioxide of Example I.
• the pressure is 3000 psig while the temperature is 30°C.
• the treatment period is about 100 minutes.
• the lenses are deblocked from the mold halves.
• the average weight percent extractables in the lenses is about 1.6.
• EXAMPLE VIII Hydrophilic contact lenses are deblocked from molds. The lenses are immersed for about 15 hours in isopropyl alcohol. The spent alcohol is replaced with fresh alcohol, and the lenses are allowed to soak again for about 8 hours. The average weight percent extractables in the lenses is about 1.1. Results are shown in Table I for comparison with Example VII.
• the lenses which are affixed to the front-curve mold halves are deblocked. Variations in deblocking occur only in lenses affixed to the base-curve mold halves.
• Examples V and VI illustrate that contact lenses may be deblocked from lens molds subsequent to polymerization steps by application of supercritical carbon dioxide/isopropyl alcohol fluids. Deblocking problems in Examples l-VI are believed to be a result of non- optimized conditions and/or fixturing problems, i.e., improper location of the lenses and mold halves within the SCF treatment cavity.
• EXAMPLE IX About 51.5 g (50 mmol) of the perfluoropolyether Fomblin® ZDOL (from Ausimont S.p.A, Milan) having a mean molecular weight of 1030 g/mol and containing 1.96meq/g of hydroxyl groups according to end-group titration is introduced into a three- neck flask together with 50mg of dibutyltin dilaurate. The flask contents are evacuated to about 20 mbar with stirring and subsequently decompressed with argon. This operation is repeated twice. About 22.2g (0.1 mol) of freshly distilled isophorone diisocyanate kept under argon are subsequently added in a counterstream of argon.
• Fomblin® ZDOL from Ausimont S.p.A, Milan
• the macromer prepared in this way is completely colourless and clear. It can be stored in air at room temperature for several months in the absence of light without any change in molecular weight.
• the filtered solution is frozen in a flask in liquid nitrogen, the flask is evacuated under a high vacuum, and the solution is returned to room temperature with the flask sealed. This degassing operation is repeated twice.
• the flask containing the macromer/comonomer solution is then transferred into a glove box with an inert gas atmosphere, where the solution is pipetted into dust-free, polypropylene contact lens molds.
• the molds are closed, and the polymerization reaction is effected by UV irradiation, with simultaneous crosslinking.
• the molds are then opened and placed in isopropyl alcohol, causing the resultant lenses to swell out of the molds.
• the lenses are extracted for about 24 hours with nearly continuous replenishing of isopropyl alcohol. Subsequently, the lenses are dried under high vacuum.
• An Autoclave Engineering model EP-2000 Supercritical CO 2 Treatment System extraction vessel is loaded with 7 lenses.
• the extraction vessel is filled with carbon dioxide and the pressure is raised to about 200 atm with a temperature of about 30°C.
• the vessel is allowed to equilibrate for about 10 minutes.
• the lenses are extracted with an 80:20 volume/volume ratio of a carbon dioxide/isopropyl alcohol (CO 2 /IPA) stream at about 200 atm and a temperature of about 30°C.
• CO 2 /IPA carbon dioxide/isopropyl alcohol
• the flow rate is held nearly constant at about 1.0 milliliters/minute.
• Extract is collected on a solid-phase adsorbent trap at about -10°C and then desorbed at about 100°C by about 3.0 milliliters of isopropyl alcohol wash per trap.
• Gravimetric analysis of extract residue collected is performed after removing isopropyl alcohol by application of a nitrogen stream under a vacuum.
• the prior extraction cycle is applied a total of 10 times.
• the process is repeated for another set of seven lenses.
• the weight percent extractables is determined by summing the weights of the extractables removed and dividing this by the sum of the extracted lens weights. This average weight percent extractables removed is about 6.0%.
• Example IX Contact lenses are prepared in accordance with (Example IX. Extraction is performed substantially as described in Example IX, with (a) a 70:30 CO 2 /IPA stream as opposed to an 80:20 stream and (b) a total number of extraction cycles of 5 rather than 10.
• the average weight percent extractables, determined in accordance with the procedure of Example IX, is about 6.1%.
• EXAMPLE XI Contact lenses are prepared in accordance with EExample IX. Extraction is performed substantially as described in Example IX, with (a) a 70:30 CO 2 /IPA stream as opposed to an 80:20 stream and (b) a total number of extraction cycles of 10.
• the average weight percent extractables, determined in accordance with the procedure of Example IX, is about 6.8%.
• EXAMPLE XII Contact lenses are prepared in accordance with Example IX. Extraction is performed substantially as described in EExample IX, with (a) a 70:30 C0 2 /IPA stream as opposed to an 80:20 stream and (b) a total number of extraction cycles of 2 rather than 10. The average weight percent extractables, determined in accordance with the procedure of Example IX, is about 4.0%.
• EXAMPLE XIII In a dry box under nitrogen atmosphere, about 200 grams of dry PDMS dipropoxyethanol (Shin-Etsu) is added to a container, isocyanatoethyl methacrylate (I EM) in an amount equal to about 2 moles per mole PDMS dialkanol is added to the container. About 0.1 weight percent dibutyltin dilaurate (DBTL) catalyst, based on PDMS dialkanol weight, is added to the container along with a stir bar. The container is immersed in an oil bath atop a stir plate, and secured in place with a clamp. A stream of UPC air at about 2 psig is passed over the mixture.
• DBTL dibutyltin dilaurate
• the mixture is agitated at room temperature (about 22°C) for about 24 hours.
• An iterative procedure follows in which the mixture is analyzed for isocyanate content and I EM is added if the PDMS dialkoxyalkanol has not been completely reacted.
• the mixture is stirred about 24 hours more.
• the macromer produced is a siloxane-containing macromer.
• a prepolymerization mixture is prepared by mixing about 56 grams of the siloxane- containing macromer, about 14 grams of TRIS, about 29 grams N,N-dimethylacrylamide (DMA), about 1 gram methacrylic acid, about 0.5 grams Darocur® 1173 photoinitiator, and about 20 grams hexanol. The mixture is agitated for about 20 minutes at room temperature.
• the mixture is degassed via a series of freezing and thawing steps.
• the container is placed in a liquid nitrogen bath until the mixture solidifies.
• a vacuum is applied to the container at a pressure of about 200 millitorr or less for about 5 minutes.
• the container is placed in a bath of room temperature water until the mixture is liquid again. This process is performed a total of three times.
• the mixture is then polymerized to form contact lenses.
• the prepolymerization mixture is poured into polypropylene contact lens molds in a nitrogen atmosphere.
• the polymerization is effected by applying UV radiation (about 4-6 mW/cm 2 ) for a period of about 15 minutes.
• the lenses are transferred into a plasma coating apparatus wherein they are surface treated in a methane/"air” mixture ("air”, as used here, denotes 79% nitrogen and 21% oxygen) for a period of about 5 minutes.
• air as used here, denotes 79% nitrogen and 21% oxygen
• Extraction of the lenses is performed substantially as described in Example IX, with (a) a 70:30 CO 2 /IPA stream as opposed to an 80:20 stream and (b) a total number of extraction cycles of 5 rather than 10.
• the average weight percent extractables, determined in accordance with the procedure of Example IX, is about 0.2%.
• the product (of ⁇ , ⁇ -bis-3-gluconamidopropyl-dimethy!polysiloxane) obtained above (about 213.3 g) is dissolved in about 800 ml of absolute THF and the solution is heated to about 40°C with the addition of catalytic amounts of dibutyltin dilaurate (DBTDL). About 29.2 g (187.5 mmol) of IEM in about 20 ml of absolute THF are added dropwise to this solution over a period of about 4 hours. This corresponds to a concentration of 1.2 equivalents of IEM per gluconamide unit.
• the reaction is carried out in the course of 48 hours (monitoring of the reaction by IR spectroscopy detection of the NCO ties).
• the reaction solution is concentrated and the product is dried in a brown glass flask under 3 Pa (0.03mbar) for 24 hours, while cooling with ice. 227.2 g of a colourless rubber-elastic product of high optical transparency remain.
• N,N-dimethylacrylamide (DMA) and 3- methacryloyloxypropyl-tris(trimethylsilyloxy)silane (TRIS) are each freed from inhibitors by distillation.
• DMA N,N-dimethylacrylamide
• TRIS 3- methacryloyloxypropyl-tris(trimethylsilyloxy)silane
• the mixture is then irradiated with a UV-A mercury high pressure lamp in a nitrogen atmosphere in a UV oven equipped for this for 5 minutes.
• the lamps (5 each of the brand TLK40W/10R, Philips) are above and below the holder inserted.
• the irradiation intensity is 14.5mW/cm 2 .
• the polypropylene mold is opened and the finished discs or lenses are removed. Extraction is performed substantially as described in EExample IX, with (a) a 100% CO 2 stream as opposed to an 80:20 CO 2 /IPA stream and (b) a total number of extraction cycles of 10.
• the average weight percent extractables, determined in accordance with the procedure of EExample IX, is about 1.6%.
• EXAMPLE XV Contact lenses are prepared in accordance with Example XIV. Extraction is performed substantially as described in Example IX, with (a) a 95:5 CO 2 /IPA stream as opposed to an 80:20 stream and (b) a total number of extraction cycles of 10. The average weight percent extractables, determined in accordance with the procedure of EExample IX, is about 1.9%.
• EEXAMPLE XVI Contact lenses are prepared in accordance with EExample XIV. ⁇ Extraction is performed substantially as described in Example IX, with (a) a 90:10 CO 2 /IPA stream as opposed to an 80:20 stream and (b) a total number of extraction cycles of 10.
• the average weight percent extractables, determined in accordance with the procedure of (Example IX, is about 2.9%.
• EEXAMPLE XVII Contact lenses are prepared in accordance with EExample XIV. ⁇ Extraction is performed substantially as described in Example IX, with (a) an 80:20 C0 2 /IPA stream and (b) a total number of extraction cycles of 10.
• the average weight percent extractables, determined in accordance with the procedure of Example IX, is about 4.7%.
• EXAMPLE XVIII Contact lenses are prepared in accordance with -Example XIV. ⁇ Extraction is performed substantially as described in (Example IX, with (a) a 70:30 CO 2 /IPA stream as opposed to an 80:20 stream and (b) a total number of extraction cycles of 10.
• the average weight percent extractables determined in accordance with the procedure of -Example IX, is about 5.6%.

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• Eyeglasses (AREA)
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• Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
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• 1995
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• 1996
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• 1997
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